Basic reaction products



Patented June 27, 1939 luNfiED'. TATE BASIC r PATENT orrics Henry Alfred Piggott and Francis Sydney Statto Imperial Chem! or amides thereof, to react with ethylene e and thereafter, if it is desired to form salts, treatingthe reaction products with acids.

- The reaction between the carboxylic acids or amides and ethylene imine may conveniently be brought about by heating the reagents together in a closed vessel, preferably in the presence of a small amount of basic catalyst such as sodi it: hydroxide or a surface-active substance such as silica gel or kieselguhr.

The temperature and duration of the heating may be varied considerably according to the particular compounds to be treated. In many cases 24) a period Y5 hours heating at 130 C. is convenlent, but heating periods as long as hours and temperatures as high as 180 C. have been used without causing discolouration or otherwise adversely aflecting the properties of the product. 26 The presence of a catalyst is not essential in every case. For example, stearlc acid has been successfully condensed with five molecules of ethylene imine in the absence of a catalyst.

The proportion of ethylene imine used may 30 likewise be varied over awide range. Quantities varying between 3 and molecular proportions of ethylene imine for each molecular proportion portions falling outside this range may likewise 85 be employed.

i As acids whichmay conveniently be used in carrying this invention into practice there may be mentioned caproic, caprylic, capric, lauric', myristic, palmitic, stearic, hydroxystearic, oleic,

40 linolei c, linolenic, ricinoleic, elaidic, undecylenic and erucic acids, likewise mixtures of these acids such as are derivable from natural oils such as coconut oil, palm oil, palm-kernel oil, rape-seed oil, linseed oil, cottonseed oil, or the acids ob- 46 tainable by fat hydrogenation processes, or the acids of waxes of vegetable, animal or mineral origin, such as beeswax, carnauba wax, montan wax, which contain esters ofv carboxylic acids with up to about 30 carbon atoms. The primary 60 amides of such acids or mixtures of acids may likewise be employed.

Reaction products made according to the invention are, in general, pale coloured oils or lowmelting solids which are soluble in organic sol- 55 vents such as. for example, benzene, chloroform general, only very of acid or amide are preferred, but proham, Blackley, Manchesten-England, minions cal Industrleo Limited, a

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- (oi. zoo-404 or ethanol. The pructs mby ing a small proportim ct cleric imine with an acid or amide ofhiah va weight areyin slightly soluble in water, but as the molecular weight of the acid or amide is shed or the proportion of ethylene imine combined with it is r the solubility of the product in water increases.

The said reaction products are ic, that is, they are capable of mill-2.1 salts with acid Salts may be formed, for example, by trea the reaction products with aqueous acids such as,

for example, aqueous hydrochloric or acetic acids. Salts may also be prepared by ole .the reaction products in a suitable organic solvent and treating the solution so'obtained with acids; this in many cases ords a convenient method of purification oi the crude reaction mirtture. Thus, for example, hydrochlorides may conveniently be prepared by 1;: r:

the reaction products in solvents such as benzene, chloroform, or ethanol and passing into the solution gaseous hydrogen chloride. According to the reaction product and solvent employed, hydro chlorides so formed either precipitate from. solution, in which case they are readily isolated by filtration, or remain dissolved and are obted in the dry solid state by evaporating 03 the solvent.-

The salts of our new be reaction products are, in general, soluble in water and these aqueous solutions are useful in textile treatment processes.

The invention is illustrated but not limited by 5.7 parts of stearic acid, i3 parts of ethylene imine (5 molecular proportions) and 0.2 port oi 8.0% aqueous sodium hydroxide are heated together in a closed vessel at 130 C. ior 5 hours. The reaction product obtained isa pale coloured, low-melting. waxy solid which, is insoluble in water but soluble in benzene or ethanol. I

For the purpose or preparing a hydrochloride the reaction product $1 part) is dissolved in hen-- zone (6 parts) and the solution is satura d with gaseous hydrogen chloride. 1 litter standing for some time the benzene is evaporated oiL'le'aving a pale coloured solid hydrochloride which is soluble in water to give foaming solutions. By using ethanolinstead of benzene as a solvent in the preparation of a hydrochloride as described above, a white solid salt precipitates, which is ref filtered oif' and dried The dry salt is soluble in water to give clear foaming solutions.

A similar reaction product is obtained by heating 5.7 parts of stearic acid with 4.3 parts of ethylene imine (5 molecular proportions) for 6 hours at 130 C. in the absence of a catalyst. It is a pale coloured low-melting waxy solid which is insoluble in water and soluble in benzene or ethanol.

' Example 2 5.7 parts of stearic acid amide, 4.3 parts of ethylene imine (5 molecular proportions) and 0.2 part of 8.0% aqueous sodium hydroxide are heated for 10 hours at 130 C. in a closed vessel. The reactionproduct is a pale coloured, low-melting solid which is insoluble in water. By dissolving the reaction product in six times its weight of ethanol and saturating the solution with hydrogen chloride, a white. solid hydrochloride precipitates, which is filtered oif and dried. The dried salt is soluble in water to give foaming solutions.

" Example 3 14.2 parts of stearic acid, 21.5 parts of ethylene imine (10 molecular proportions) and 0.5 part of 8.0% aqueous sodium hydroxide are heated in a closed vessel for hours at 140 C. The reaction product so obtained is a low-melting, pale coloured waxy solid which is soluble in water. Dry gaseous hydrogen chloride is passed through a solution of the reaction product (1 part) in a mixture of ethanol (7 parts) and acetone (3 parts) The hydrochloride is obtained as a granular powder and is filtered off and dried; it is a cream coloured, slightly hygroscopic solid which is soluble in water to give clear foaming solutions.

Example 4 tained reaction product is a pale yellow clear viscous mass which is soluble in water to give forming solutions. By dissolving the reaction product in nine times its weight of ethanol and saturating the solution with dry gaseous hydrogen chloride a white, slightly sticky precipitate of the hydrochloride is obtained. By decanting the mother liquor and grinding the precipitate with acetone a white granular solid is obtained which is illtered oil and dried. It is hygroscopic and dissolves readily in water togive clear foaming solutions.

'Example 5 2.25 parts of mixed coconut oil fatty acids, 12.9 parts of ethylene imine (30 molecular proportions) and 0.3 part of 8.0% droxide are heated together in a closed .vessel at 180 C. for 20 hours. After cooling 3.9 parts (9 molecular proportions) of unreacted ethylene imine are removed by distillation (if necessary under reduced pressure). The basic reaction product so obtained is a yellow, low-melting, gelatinous mass which dissolves readily in water to give foaming solutions. By dissolving the reaction product (1 part) in a mixture of ethanol (9 parts) and acetone (9 parts) and passing dry gaseous hydrogen chloride through the solution, a gummy precipitate of the hydrochloride is obtained. This is filtered ofi and dried under reduced pressure. It is then a fawn coloured brittle hygroscopic mass, very soluble in water to give clear foaming solutions.

-action product (1 aqueous sodium hy-.

Example 6 9.5 parts of stearic acid, 4.3 parts of ethylene imine (3 molecular proportions) and 0.2 part of 8.0% aqueous sodium hydroxide are heated to-' gether in a closed vessel for 5 hours at 130 C. The reaction product so obtained is a pale-coloured, low-melting waxy solid almost insoluble in water and soluble in ethanol or'acetone. The repart) is dissolved in a mixture of ethanol (6 parts) and acetone (3 parts) at C. and dry gaseous hydrogen chloride is passed through the solution, when the hydrochloride is precipitated as a cream-coloured powder. It is readily soluble in water to give clear foaming solutions.

Example 7 10.0 parts of lauric acid, 6.5 parts of ethylene imine (3 molecular proportions) and 0.3 part of 30% aqueous sodium hydroxide are heated together in'a closed vessel for 6 hours at 130 C. The reaction product so obtained is a cream-coloured, low-melting waxy solid, slightly soluble in cold water and moderately soluble on warming; it is readily soluble in ethanol or acetone. By dissolving the reaction product (1 part) in 6 parts of acetone and saturating the solution with dry gaseous hydrogen chloride a cream coloured precipitate of the hydrochloride is obtained.- It is very hygroscopic and dissolves readily in water to give clear foaming solutions.

We claim:

1. A process for the manufacture of new basic reaction products which comprises heating a compound selected from the group consisting of aliphatic carboxylic acids containing at least six carbon atoms and the primary amides of said acids with at least 3 molecular proportions of ethylene imine.

2. A process according to claim 1 wherein the reactants are heated together for at least 5 hours at temperatures of about 130 C. or more in the presence of catalytic proportions of sodium hydroxide.

3. A process according to claim 1 wherein the basic reaction products are dissolved in an organic solvent and gaseous hydrogen chloride is passed through said solution to obtain the hydrochlorides of the basic reaction products.

4. Chemical products of the group consisting of basic reaction products which are obtained by heating a compound selected from the group consisting of aliphatic carboxylic acids containing at least six carbon atoms and the primary amides of said acids with at least 3 molecular proportions of ethylene imine and the acetates and hydrochlorides of said basic reaction products.

5. Chemical products of the group consisting of basic reaction products which are obtained by,

heating an aliphatic carboxylic acid containing at least six carbon atoms with at least 3 molecular proportions of ethylene imine and the acetates and hydrochlorides of said basic reaction products.

6. Basic reaction products obtained by causing an aliphatic carboxylic acid containing at least six carbon atoms to react at elevated temperature with at least 3 molecular proportions of ethylene imine in the presence of catalytic proportions of sodium hydroxide.

7. Hydrochloride; of the basic reaction products defined-in claim 6.

8. Chemical products of the group consisting of basic reaction products by heating a primary amide which are obtained of an aliphatic carboxylic acid containing at least six carbon atoms 10. A basic reaction product obtained by heatwith at least 3 molecular proportions of ethylene ing stearic acid with at least 3 molecular proimine and the acetates and hydrochlorides of portions of ethylene imine in the presence of said basic reaction products. catalytic proportions of sodium hydroxide.

9. Basic reaction products obtained by caus- 11. A basic reaction product obtained by heat- 5 ing a primary amide or an aliphatic carboxylic ing stearic acid amide with at least 3 molecular acid containing at least six carbon atoms to reproportions of ethylene imine in the presence of act at elevated temperature in the presence of a catalytic proportions of sodium hydroxide. catalytic proportion of sodium hydroxide with HENRY ALFRED PIGGOTT.

19 at least 3 molecular propo rtions of ethylene imine. FRANCIS SYDNEY STATHAM. 1 I 

